WO2020078553A1 - Electrochemical system for the synthesis of aqueous oxidising agent solutions - Google Patents

Electrochemical system for the synthesis of aqueous oxidising agent solutions Download PDF

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Publication number
WO2020078553A1
WO2020078553A1 PCT/EP2018/078559 EP2018078559W WO2020078553A1 WO 2020078553 A1 WO2020078553 A1 WO 2020078553A1 EP 2018078559 W EP2018078559 W EP 2018078559W WO 2020078553 A1 WO2020078553 A1 WO 2020078553A1
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Prior art keywords
solution
container
oxidizing agent
salt
catholyte
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PCT/EP2018/078559
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German (de)
French (fr)
Inventor
Vitold Bakhir
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Blue Safety Gmbh
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Application filed by Blue Safety Gmbh filed Critical Blue Safety Gmbh
Priority to CA3117252A priority Critical patent/CA3117252A1/en
Priority to JP2021521007A priority patent/JP7026985B2/en
Priority to PCT/EP2018/078559 priority patent/WO2020078553A1/en
Priority to ES18807868T priority patent/ES2916459T3/en
Priority to EP18807868.7A priority patent/EP3867422B1/en
Priority to EA202100115A priority patent/EA039722B1/en
Priority to CN201880098779.1A priority patent/CN112912544B/en
Priority to US17/286,141 priority patent/US11858833B2/en
Publication of WO2020078553A1 publication Critical patent/WO2020078553A1/en

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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C02F1/4674Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation with halogen or compound of halogens, e.g. chlorine, bromine
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/02Hydrogen or oxygen
    • C25B1/04Hydrogen or oxygen by electrolysis of water
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/13Ozone
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/24Halogens or compounds thereof
    • C25B1/26Chlorine; Compounds thereof
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/28Per-compounds
    • C25B1/30Peroxides
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/34Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • C25B1/46Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00Operating or servicing cells
    • C25B15/02Process control or regulation
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00Operating or servicing cells
    • C25B15/08Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/083Separating products
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00Operating or servicing cells
    • C25B15/08Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/085Removing impurities
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00Operating or servicing cells
    • C25B15/08Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/087Recycling of electrolyte to electrochemical cell
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/001Processes for the treatment of water whereby the filtration technique is of importance
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/42Treatment of water, waste water, or sewage by ion-exchange
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00Apparatus for treatment of water, waste water or sewage
    • C02F2201/46Apparatus for electrochemical processes
    • C02F2201/461Electrolysis apparatus
    • C02F2201/46105Details relating to the electrolytic devices
    • C02F2201/46115Electrolytic cell with membranes or diaphragms
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00Apparatus for treatment of water, waste water or sewage
    • C02F2201/46Apparatus for electrochemical processes
    • C02F2201/461Electrolysis apparatus
    • C02F2201/46105Details relating to the electrolytic devices
    • C02F2201/46155Heating or cooling
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00Apparatus for treatment of water, waste water or sewage
    • C02F2201/46Apparatus for electrochemical processes
    • C02F2201/461Electrolysis apparatus
    • C02F2201/46105Details relating to the electrolytic devices
    • C02F2201/4618Supplying or removing reactants or electrolyte
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00Apparatus for treatment of water, waste water or sewage
    • C02F2201/46Apparatus for electrochemical processes
    • C02F2201/461Electrolysis apparatus
    • C02F2201/46105Details relating to the electrolytic devices
    • C02F2201/4618Supplying or removing reactants or electrolyte
    • C02F2201/46185Recycling the cathodic or anodic feed

Definitions

  • the invention relates to the field of chemical technology and relates in particular to devices for the electrolysis of aqueous alkali metal chloride solutions for the production of chlorine, chlorine compounds, oxygen, ozone and hydroperoxide compounds and can be used for disinfection in medicine, pharmacy and food industry as well as in cleaning and the sterilization of water by aqueous solutions of chlorine oxygen and hydroperoxide oxidants.
  • the solutions of chlorine oxygen and hydroperoxide compounds are obtained in the electrolysis of aqueous alkali metal chloride solutions by dissolving products of anodizing chloride solutions in water, mostly sodium chloride solutions, in the membrane or diaphragm method.
  • Conventional processes in the electrolysis technology of aqueous sodium chloride solutions are the purification of aqueous starting sodium chloride solutions from hardening agents, heavy metals and admixtures of organic compounds, all of which occur in starting rock salt and are extremely difficult with traditional processing methods from salt intended for use, e.g. B. in the food industry to be removed.
  • various auxiliary devices are used for the electrochemical synthesis, which are referred to in their entirety as a technical electrochemical system.
  • Most technical electrochemical systems include, in addition to the actual electrochemical reactor, which consists of a membrane or diaphragm electrolysis apparatus with an external separator tank, heat exchangers, regulators for the pressure and flow rate of liquids and gases, additional devices for producing and cleaning the saline solution of hardening agents , multivalent metal ions, organic admixtures as well as ion exchange or reverse osmosis systems for cleaning the water from hardening agents as well as collecting containers for the products of electrochemical synthesis, in particular soda acoustic and hypochlorite solutions.
  • the actual electrochemical reactor which consists of a membrane or diaphragm electrolysis apparatus with an external separator tank, heat exchangers, regulators for the pressure and flow rate of liquids and gases, additional devices for producing and cleaning the saline solution of hardening agents , multivalent metal ions, organic admixtures as well as ion exchange or reverse osmosis systems for cleaning the water from hardening agents as well as collecting containers for the products of
  • This process is carried out using a technical electrochemical system that In addition to the membrane electrolysis apparatus, it also includes a salt dissolving tank, the task of which is to integrate the processes of salt storage and the production of the actual concentrated salt solution, which is simultaneously used by hardening agents and multivalent metals by converting the soluble compounds into insoluble hydroxides by metered introduction of catholyte into the saline solution is cleaned. In this container, the salt solution is cleaned of organic admixtures by the metered introduction of hydrogen peroxide solution.
  • the technical electrochemical system which realizes the claimed method also includes an activated carbon filter and a filter with ion exchange resin for removing the residual amounts of multivalent cations, which are arranged one after the other in the feed line for the salt solution to the electrolysis apparatus.
  • the metered introduction of hydrochloric acid into the supply line for the saline solution to the electrolysis apparatus is provided in order to avoid a harmful effect of the hypercaustic saline solution on the anode coating and the unproductive electrical energy expenditure for the oxidation of the hydroxide ions and the mass transfer of monovalent sodium cations through the membrane in to reduce the cathode space.
  • a disadvantage of the technical solution according to patent RU 2 509 829 C2 is the need to use various additional reagents for reprocessing the ion exchange filter, for oxidizing the organic compounds in the salt solution, for correcting the pH of the salt solution that gets into the anode compartment of the electrolysis apparatus, as well as in the necessary periodic replacement of the carbon filter bed.
  • this electrochemical system often has to be maintained, constantly checked and its operating parameters corrected.
  • the device chosen as the prototype according to US Pat. No. 7,897,023 B2 is closest to the technical nature and the result to be achieved.
  • This device represents an electrochemical system comprising a diaphragm electrolysis apparatus with a ceramic tubular ultrafiltration diaphragm, with a catholyte and anolyte circulation circuit with corresponding separating tanks for separating electrolysis gases and with heat exchanger devices for cooling the catholyte and anolyte
  • a disadvantage of this device is that multivalent ions, including heavy metal ions, are present in the finished product, ie in the solution of chlorine oxygen and hydroperoxide oxidants in water. These ions usually occur in drinking water or natural fresh water, which is used for the preparation of the starting salt solution and for the recovery of the oxidizing agent solution by dissolving the gaseous products of the electrochemical anode reactions in the fresh water stream, which contain microdrops of moisture with dissolved singlet oxygen, ozone and hydrogen peroxide . Multivalent metal ions, and especially heavy metal ions, are known to be catalysts for the chemical decomposition of active chlorine and active oxygen compounds - hypochlorous acid and hydrogen peroxide.
  • the object of the invention is to increase the time over which the biocidal properties of the end product, the oxidizing agent solution, are obtained by cleaning the water from hardening agents and multivalent metal diodes, and the time for the continuous or repeated short-term operation of the electrochemical system between the maintenance operations extend without having to correct its operating parameters by cleaning the salt solution from organic admixtures while completely avoiding the consumption of additional chemical reagents.
  • the technical result of the invention is achieved in that, in contrast to the known technical solution, when the water enters the device for mixing the fresh water stream with the gaseous oxidizing agents, a filter is arranged in front of which A supply line for the fresh water is a device for the metered introduction of the catholyte from the separating container of the cathode circuit into the water flow and the salt in the device for the supply of the salt solution into the anode compartment by means of the metered introduction of the oxidizing agent solution from the collecting container into the container of the salt dissolving device is solved, at the output of which a filter is arranged, which is connected to the input of the metering pump for supplying the salt solution under pressure into the anode compartment of the electrolysis apparatus.
  • FIG. 1 shows the basic hydraulic circuit diagram of the electrochemical system for the synthesis of the oxidizing agent solution from alkali metal chlorides, preferably sodium chloride.
  • the electrochemical system includes a diaphragm electrolysis apparatus electrochemical reactor (1) with coaxially arranged electrodes - the anode (2), the cathode (3) and the diaphragm (4).
  • the procedural scheme of the anode synthesis of the oxidizing agents consists of the anode compartment (5) of the reactor (1), the input of which is connected via the check valve (6) to the outlet of the flosh pressure metering pump (7), the input of which in turn is connected to the filter (8) connected to the container for dissolving the salt (9), in which the starting salt solution is prepared and purified.
  • the outlet of the anode compartment (5) is connected to the separating container (10) for separating the gaseous products of the electrochemical anode reactions from the anolyte.
  • the outlet in the lower part of the separating tank (10) is connected to the inlet of the anode compartment (5) of the electrochemical reactor (1), the anode circuit of the anolyte thereby being closed.
  • the outlet in the upper part of the separating container (10) is connected via the check valve (11) to the device (12) for dissolving the gaseous products of the electrochemical anode reactions in fresh water.
  • the output of the device (12) is connected to the upstream pressure regulator (13) which, when the electrochemical system is in operation, ensures that the pressure in the anode circuit of the electrochemical reactor (1) is constantly exceeded by the pressure in the cathode circuit by building up a regulated, predetermined hydraulic resistance in the oxidant solution stream .
  • the hydraulic line which connects the outlet of the device (12) with the admission pressure regulator (13), there is a sensor for the conductivity of the
  • Oxidizing agent solution "X s " arranged.
  • the output of the pre-pressure regulator (13) is connected to the input of the collecting container for the oxidizing agent solution (14), which is equipped with sensors for the permissible maximum (15) and minimum (16) level of the oxidizing agent solution.
  • One of the outputs of the collecting container for the oxidant solution (14) is with the entrance of the container (9) for producing and cleaning the saline solution, which is lower than the collecting container of the oxidizing agent solution (14).
  • the other outlet of the container (14) is connected to the inlet of the metering pump (17), which is intended for the supply of the oxidizing agent solution to the application, for. B. at the point of incorporation of the oxidizing agent into the water supply system to sanitize the drinking water.
  • the water enters the device (12) for dissolving the gaseous products of the electrochemical anode reactions via the check valve (18) and the heat exchange system of the anode circuit of the electrochemical reactor (1) from the outlet of the filter (19).
  • the hydraulic line which connects the outlet of the heat exchange system of the anode circuit of the electrochemical reactor (1) and the inlet of the check valve (18)
  • the water which has passed through the heat exchange device (20) of the cathode circulation circuit is fed with an addition of catholyte from the separation circulation container of the catholyte (21).
  • the catholyte is introduced into the water flow at the outlet from the heat exchange device of the cathode circulation circuit (20) by means of a metering pump (22).
  • a sensor for the conductivity of the outlet water “X” is arranged before the point of introduction of the catholyte from the separating circulation container of the catholyte (21).
  • the cathode circuit of the catholyte comprises the cathode chamber (23) of the electrochemical reactor (1), the circulation pump (24) and the valve (25) Filling the recycle circulation tank of the catholyte (21) when the system is started up and purified water is fed in when the system is in operation.
  • the separating circulation tank of the catholyte (21) is provided with a drain line of the catholyte, which is formed during operation of the system. The water is fed to the electrochemical system for the synthesis of the oxidizing agent solution from the pressurized water supply network via the coarse filter (pre-filter) (26), the electromagnetic valve (27) and the secondary pressure regulator (28).
  • the electrochemical system for synthesizing the oxidant solution works as follows.
  • the container (9) with hard salt is added in the amount required for the synthesis of the specified amount of oxidizing agent solution in a ratio of maximum consumption of 0.8 Grams of salt filled per 1 liter of oxidizing agent solution.
  • the container (9) must be filled with 20 kilograms of salt.
  • the container (9) is filled with purified and softened water, the salt having to be completely covered with water. This is done once, when the system is started up for the first time.
  • the connection for the water supply at the entrance of the mechanical filter (26) is connected to the pressure line for the fresh water (drinking water).
  • the normally closed electromagnetic valve (27) is supplied with voltage by means of a separate switch.
  • the specified volume flow of water through the system and the specified pressure in the anode circuit are set by a secondary pressure regulator (28) and a pre-pressure regulator (13), based on the display values of the pressure gauge M and the external flow meter (not shown on the drawing) .
  • valve (25) we fill the separating tank of the catholyte (21) with water until the water jet comes out of the drain line of the separating tank (21), then the valve is brought into a position which ensures that water enters the separating circulation tank for the Catholyte (21) is fed at a rate of 20-30 drops per minute (is determined on the basis of the speed of the drop of the drop from the drain line of the separating container for the catholyte (21)).
  • the metering pump (7) is switched on and the anode compartment (5) of the electrochemical reactor (1) is filled with salt solution from the container (9). The end of the filling process is determined by increasing the sensor values for the
  • Oxidizing agent solution "X s " and the source water “X” is connected.
  • the catholyte circulation pump (24) the pump (22) for the metered introduction of the catholyte into the fresh water stream and the metering pump (7) for the supply of the salt solution into the anode compartment (5) of the electrochemical reactor (1).
  • the main reaction in the electrochemical reactor (1) is the release of molecular chlorine in the anode compartment (5) and the formation of sodium hydroxide in the cathode compartment (23):
  • the chlorine dioxide is synthesized directly from the salt solution and from the hydrochloric acid in the anode compartment with a lower current yield, which occurs when the molecular chlorine is dissolved near the anode forms:
  • Ozone forms in the anode compartment of the reactor through direct water decomposition and through oxidation of the released oxygen:
  • Hydrogen peroxide increases with a decrease in the mineral content of the aqueous sodium chloride starting solution and reaches 20-30% with a salt concentration in the starting solution Range 80 - 150 g / l with an anode density of five to seven thousand amperes per square meter (5000 - 7000 A / m 2 ).
  • Increasing the salt content in the starting solution to 250-300 g / l reduces the current efficiency of the formation reactions of chlorine dioxide, ozone, singlet oxygen and hydrogen peroxide to 1-2% with an anode density of 5000-7000 A / m 2 and to 0. 1 - 0.2% with an anode density of 2000 - 3000 A / m 2 .
  • hypochlorous acid the amount of which in the solution is limited by the falling pH due to the formation of hydrochloric acid
  • the pH value can be adjusted by adding alkali lye, i.e. H. e.g. As sodium hydroxide can be changed.
  • alkali lye i.e. H. e.g. As sodium hydroxide can be changed.
  • sodium hypochlorite as a salt of a weak acid (hypochlorous acid) and a strong base (sodium hydroxide) has a 250 to 350 times reduced antimicrobial activity compared to hypochlorous acid.
  • the formation of sodium hypochlorite can be accompanied by a simultaneous increase in the pH of the oxidizing agent solution with a simultaneous increase in the concentration of the hypochlorous acid and removal of the hardening agents and the multivalent metal ions, and the like.
  • a. of iron can be avoided by introducing catholyte containing free hydroxyl groups into the water flow.
  • the catholyte has an extremely high chemical adsorption activity in hydrate formation reactions.
  • the increased reactivity of the catholyte is explained, among other things, by the large amount of free hydroxyl groups and dissolved hydrogen contained in the catholyte.
  • the hydroxides and the flakes formed - the particle aggregates of the hydroxides with the adsorbed molecules of organic compounds, the microcolloid particles and hydrogen bubbles and the water which has been purified and freed from multivalent metal cations and which contains low concentrations of dissolved hydrogen and free hydroxyl groups, are separated off on the filter (19) , flows into the device for dissolving the oxidizing agents (12), these cause an increase in the concentration of hypochlorous acid in the oxidizing agent solution in accordance with the following reaction: Cl 2 + H 2 0 + OH- -> 2HOCI.
  • the oxidizing agent solution is also used, in addition to its main purpose, in small quantities as an agent for dissolving the salt in the container (9), which oxidatively decomposes the organic admixtures that originally contained in the rock salt and are difficult to remove in conventional domestic salt manufacturing processes and numerous industrial applications.
  • the oxidized and coagulated organic foreign compounds are retained by the filter (8) at the outlet of the container (9).
  • the dissolution of the salts by the oxidizing agent solution makes it possible to ensure the microbiological purity of the agent in the salt dissolving tank. As a result, it no longer has to be regularly waited until the end of the process of dissolving the entire filled amount of salt.
  • the tests with the electrochemical system were carried out in comparison with the prototype of the device, which was carried out according to US Pat. No. 7,897,023 B2 and was supplemented with an ion exchanger (water softener) and with a container for dissolving the salt and for producing a saline solution.
  • an ion exchanger water softener
  • the water from the ion exchange softener was used not only to produce the salt solution, but also to dissolve the gaseous products of the anode compartment of the electrochemical reactor.
  • the ion exchange softener was connected to the drinking water pressure line.
  • the device according to the US patent was also supplemented with a collecting container for the oxidizing agent solution.
  • Both comparable systems contained an electrochemical reactor which consisted of four electrochemical modular elements (cells) according to patent EP 0 842 122 B1.
  • the aqueous starting salt solution contained 250 g / l sodium chloride, the hardness content in the starting solution was 0.3 MG-QKB / P (1 da corresponds to 0.3566 MG-QKB / P in the electrochemical system according to US Pat. No. 7,897,023 B2 and 4 , 5 MG-QKB / P in the tank (9) of the system according to the new technical solution
  • the reason for the difference was the low level of hardness in water after the ion exchange softener and the significantly higher level of hardness in conventional tap drinking water which originally produced the starting salt solution in the electrochemical system according to the new technical solution.
  • the current through the electrochemical reactor in the prototype device was 40 amperes at a voltage of 5 volts.
  • the same values were used for the electrochemical reactor in the electrochemical system according to the new Accordingly, 52 g / h of oxidizing agents were produced in each comparison system
  • the oxidant solution which was produced in the prototype system at a speed of 100 l / h, had an oxidant concentration of 500 mg / l, a pH of 2.8 and a total mineral content of 0.86 g / l.
  • the hardness-forming agent content in the oxidizing agent solution was 0.2 MG-QKB / P.
  • the pH value of the solution at the outlet increased to 6.0, while the mineral content of the solution was increased to 1.5 g / l.
  • the oxidant solution which is produced at a rate of 100 l / h in the device according to the new technical solution, had a pH of 3.0 at an oxidant concentration of 500 mg / l and a total mineral content of 0.66 g / l .
  • the pH value of the oxidizing agent solution increased while the mineral content increased to 0.82 g / l.
  • the hardness of the oxidizing agent solution was in the range of 0.8 MG-QKB / P, but decreased to 0.6 MG-QKB / P in the course of 2 hours of operation.
  • the evaluation of the results of these investigations shows that the introduction of catholyte in front of the filter (19) significantly reduces the hardness of the water for dissolving the gaseous products of the anodization of the sodium chloride solution and that the introduction of the oxidizing agent solution with a reduced content of hardening agents in the container (9 ) for the production of the salt solution, the content of hardness in the oxidizing agent solution is significantly reduced.
  • the solution from the system according to the new technical solution had the following values after 20 hours of operation of the system: pH 5.9; Oxidizer concentration 510 mg / l; Total mineral content 0.83 g / l.
  • the oxidant concentration in the sample (solution sample) taken was unchanged.
  • the hardness content in the oxidant solution of the prototype was 0.6 MG-QKB / P, ie the introduction of catholyte into the starting water in front of the filter made it possible to purify the water from hardness builders. As a result, the oxidizing agents remained in the solution for longer.
  • the solution from the prototype system showed the following values after one hundred hours of operation of the system: pH 6.3; Oxidant concentration 470 mg / l; Total mineral content 1.4 g / l. After 10 days, the oxidant concentration in the sample taken (amount of the solution 1 liter) decreased to 440 mg / l. The hardness level in the prototype's oxidant solution was 3.8 MG-QKB / P, which is obviously related to the significant deterioration in the function of the ion exchange filter.
  • the solution from the system according to the new technical solution had the following values after one hundred hours of operation: Values: pH 5.9; Oxidizing agent concentration 500 mg / l; Total mineral content 0.83 g / l.
  • the oxidant concentration in the sample taken was unchanged.
  • the content of hardening agents in the oxidizing agent solution from the system according to the new technical solution was 0.6 MG-QKB / P, ie the introduction of catholyte into the starting water before the filter made it possible to purify the water effectively from hardening agents over a long period of time . This kept the oxidizing agents in the solution longer.
  • Examination of the containers for the solution of the salt and the production of the salt solution showed a biofilm of microorganisms in the container of the prototype system. The biofilm was completely missing in the container (9) of the system according to the new technical solution.

Abstract

The invention concerns the field of chemical technology and relates in particular to devices for the electrolysis of aqueous alkali metal chloride solutions to obtain chlorine, chlorine compounds, oxygen, ozone, and hydroperoxide compounds and can be used for disinfection in the medical, pharmaceutical, and food industry and in the purification and sterilisation of water by means of aqueous solutions of chlorine-oxygen oxidants and hydroperoxide oxidants.

Description

Elektrochemisches System zur Synthese von wässriger Oxidationsmittel-Lösung  Electrochemical system for the synthesis of aqueous oxidizing agent solution
Die Erfindung bezieht sich auf das Gebiet der chemischen Technologie und betrifft insbesondere Vorrichtungen zur Elektrolyse von wässrigen Alkalimetallchlorid-Lösungen zur Gewinnung von Chlor, Chlorverbindungen, Sauerstoff, Ozon sowie Hydroperoxidverbindungen und kann zur Desinfektion in der Medizin, Pharmazie, und Lebensmittelindustrie sowie bei der Reinigung und der Keimfreimachung von Wasser durch wässrige Lösungen von Chlorsauerstoff- und Hydroperoxidoxidantien eingesetzt werden. The invention relates to the field of chemical technology and relates in particular to devices for the electrolysis of aqueous alkali metal chloride solutions for the production of chlorine, chlorine compounds, oxygen, ozone and hydroperoxide compounds and can be used for disinfection in medicine, pharmacy and food industry as well as in cleaning and the sterilization of water by aqueous solutions of chlorine oxygen and hydroperoxide oxidants.
Die Lösungen der Chlorsauerstoff- und Hydroperoxidverbindungen werden bei der Elektrolyse wässriger Alkalimetallchlorid-Lösungen durch Lösen von Produkten der Anodisierung von Chloridlösungen in Wasser, zumeist Natriumchloridlösungen, im Membran- bzw. Diaphragma- Verfahren gewonnen. Herkömmliche Prozesse in der Elektrolyse-Technologie von wässrigen Natriumchloridlösungen sind die Reinigung wässriger Ausgangsnatriumchloridlösungen von Härtebildnern, Schwermetallen und Beimengungen organischer Verbindungen, die durchweg in Ausgangssteinsalz Vorkommen und äußerst schwierig mit traditionellen Aufbereitungsverfahren aus zur Verwendung bestimmtem Salz, z. B. in der Lebensmittelindustrie, zu entfernen sind. Für die elektrochemische Synthese werden neben der Hauptvorrichtung, dem Elektrolyseapparat, verschiedene Hilfsvorrichtungen eingesetzt, die in ihrer Gesamtheit als technisches elektrochemisches System bezeichnet werden. Die meisten technischen elektrochemischen Systeme umfassen neben dem eigentlichen elektrochemischen Reaktor, der aus einem Membran- bzw. Diaphragma-Elektrolyseapparat mit externem Abscheidebehälter, Wärmetauschern, Reglern für den Druck und die Durchflussmenge von Flüssigkeiten und Gase besteht, Zusatzeinrichtungen zur Herstellung und Reinigung der Salzlösung von Härtebildnern, multivalenten Metallionen, organischen Beimischungen sowie lonenaustausch- bzw. Umkehr-Osmoseanlagen zur Reinigung des Wassers von Härtebildnern sowie Sammelbehälter für die Produkte der elektrochemischen Synthese, insbesondere Sodakaustik- und Hypochloritlösungen. The solutions of chlorine oxygen and hydroperoxide compounds are obtained in the electrolysis of aqueous alkali metal chloride solutions by dissolving products of anodizing chloride solutions in water, mostly sodium chloride solutions, in the membrane or diaphragm method. Conventional processes in the electrolysis technology of aqueous sodium chloride solutions are the purification of aqueous starting sodium chloride solutions from hardening agents, heavy metals and admixtures of organic compounds, all of which occur in starting rock salt and are extremely difficult with traditional processing methods from salt intended for use, e.g. B. in the food industry to be removed. In addition to the main device, the electrolysis apparatus, various auxiliary devices are used for the electrochemical synthesis, which are referred to in their entirety as a technical electrochemical system. Most technical electrochemical systems include, in addition to the actual electrochemical reactor, which consists of a membrane or diaphragm electrolysis apparatus with an external separator tank, heat exchangers, regulators for the pressure and flow rate of liquids and gases, additional devices for producing and cleaning the saline solution of hardening agents , multivalent metal ions, organic admixtures as well as ion exchange or reverse osmosis systems for cleaning the water from hardening agents as well as collecting containers for the products of electrochemical synthesis, in particular soda acoustic and hypochlorite solutions.
Bekannt ist ein Verfahren zur Gewinnung von Produkten der Elektrolyse von Natriumchloridlösungen in einem technischen elektrochemischen System, das im Patent RU 2 509 829 C2 beschrieben ist. A method is known for obtaining products for the electrolysis of sodium chloride solutions in a technical electrochemical system, which is described in patent RU 2 509 829 C2.
Dieses Verfahren wird mit Hilfe eines technischen elektrochemischen Systems ausgeführt, das neben dem Membran-Elektrolyseapparat einen Salzlösebehälter umfasst, dessen Aufgabe es ist, die Prozesse der Salzlagerung und der Herstellung der eigentlichen konzentrierten Salzlösung zu integrieren, wobei diese gleichzeitig von Härtebildnern und multivalenten Metallen durch Umwandlung der löslichen Verbindungen in unlösliche Hydroxide durch dosierte Einbringung von Katholyt in die Salzlösung gereinigt wird. In diesem Behälter wird die Salzlösung von organischen Beimischungen durch dosierte Einbringung von Wasserstoffperoxid-Lösung gereinigt. Das technische elektrochemische System, das das beanspruchte Verfahren realisiert, beinhaltet ebenfalls einen Aktivkohle-Filter und einen Filter mit lonenaustauschharz zur Entfernung der Restmengen an multivalenten Kationen, die hintereinander in der Zuführungsleitung für die Salzlösung zum Elektrolyseapparat angeordnet sind. Nach dem Ionenaustauschfilter ist die dosierte Einbringung von Salzsäure in die Zuführungsleitung für die Salzlösung zum Elektrolyseapparat vorgesehen, um eine schädliche Wirkung der hyperkaustischen Salzlösung auf die Anodenbeschichtung zu vermeiden und den unproduktiven Elektroenergieaufwand für die Oxydation der Hydroxidionen sowie den Stofftransport von monovalenten Natriumkationen durch die Membran in den Kathodenraum zu verringern. This process is carried out using a technical electrochemical system that In addition to the membrane electrolysis apparatus, it also includes a salt dissolving tank, the task of which is to integrate the processes of salt storage and the production of the actual concentrated salt solution, which is simultaneously used by hardening agents and multivalent metals by converting the soluble compounds into insoluble hydroxides by metered introduction of catholyte into the saline solution is cleaned. In this container, the salt solution is cleaned of organic admixtures by the metered introduction of hydrogen peroxide solution. The technical electrochemical system which realizes the claimed method also includes an activated carbon filter and a filter with ion exchange resin for removing the residual amounts of multivalent cations, which are arranged one after the other in the feed line for the salt solution to the electrolysis apparatus. After the ion exchange filter, the metered introduction of hydrochloric acid into the supply line for the saline solution to the electrolysis apparatus is provided in order to avoid a harmful effect of the hypercaustic saline solution on the anode coating and the unproductive electrical energy expenditure for the oxidation of the hydroxide ions and the mass transfer of monovalent sodium cations through the membrane in to reduce the cathode space.
Ein Nachteil der technischen Lösung gemäß Patent RU 2 509 829 C2 besteht im notwendigen Einsatz verschiedener zusätzlicher Reagenzien zur Wiederaufbereitung des Ionenaustauschfilters, zur Oxydation der organischen Verbindungen in der Salzlösung, zur Korrektur des pH-Wertes der Salzlösung, die in den Anodenraum des Elektrolyseapparates gelangt, sowie in der notwendigen periodischen Auswechselung des Kohlefilterbetts. Diesbezüglich muss dieses elektrochemische System häufig gewartet, ständig kontrolliert und dessen Betriebsparameter korrigiert werden. A disadvantage of the technical solution according to patent RU 2 509 829 C2 is the need to use various additional reagents for reprocessing the ion exchange filter, for oxidizing the organic compounds in the salt solution, for correcting the pH of the salt solution that gets into the anode compartment of the electrolysis apparatus, as well as in the necessary periodic replacement of the carbon filter bed. In this regard, this electrochemical system often has to be maintained, constantly checked and its operating parameters corrected.
Dem technischen Wesen und dem zu erzielenden Ergebnis ist die als Prototyp gewählte Vorrichtung gemäß Patent US 7 897 023 B2 am nächstliegenden. Diese Vorrichtung stellt ein elektrochemisches System dar, das einen Diaphragma-Elektrolyseapparat mit einem keramischen röhrenförmigen Ultrafiltrations-Diaphragma, mit Katholyt- und Anolyt-Umlaufkreis mit entsprechenden Abscheidebehältern zur Abscheidung von Elektrolyse-Gasen und mit Wärmetauschervorrichtungen zur Kühlung des Katholyts und Anolyts, eine aus einer Dosierpumpe mit Salzlösebehälter bestehende Vorrichtung für die Zuführung der gereinigten Salzlösung unter Druck in den Anodenraum, eine Vorrichtung zum Lösen der feuchten gasförmigen Produkte der elektrochemischen Anodenreaktionen im Wasserstrom zur Gewinnung der Oxidationsmittellösung, eine Vorrichtung zur Überdruckstabilisierung im Anodenraum, einen Sammelbehälter für die Oxidationsmittellösung sowie eine Einrichtung für die dosierte Einbringung von Katholyt aus dem Abscheidebehälter des Kathodenkreises in die zu synthetisierenden Oxidationsmittellösung umfasst. Ein Nachteil dieser Vorrichtung besteht darin, dass multivalente Ionen, u. a. Schwermetallionen, im Fertigprodukt, d. h. in der Lösung von Chlorsauerstoff- und Hydroperoxidoxidantien in Wasser vorhanden sind. Diese Ionen kommen gewöhnlich in Trinkwasser bzw. natürlichem Süßwasser vor, das für die Herstellung der Ausgangssalzlösung sowie zur Gewinnung der Oxidationsmittellösung durch Lösen der gasförmigen Produkte der elektrochemischen Anodenreaktionen im Süßwasserstrom, die Mikrotropfen von Feuchtigkeit mit darin gelösten Singulettsauerstoff, Ozon und Wasserstoffperoxid enthalten, verwendet wird. Bekanntlich sind multivalente Metallionen, und besonders Schwermetallionen, Katalysatoren für die chemische Zersetzung von Aktivchlor- und Aktivsauerstoffverbindungen - hypochloriger Säure und Wasserstoffperoxid. Aus diesem Grund verlieren die in dieser Vorrichtung hergestellten Oxidationsmittellösungen ihre Bioaktivität innerhalb weniger Tage infolge der Selbstzersetzung unter Einwirkung katalytisch aktiver Ionen. Ein weiterer Nachteil dieser technischen Lösung ist die notwendige periodische Reinigung der Elektrodenräume des elektrochemischen Reaktors von oxidierten organischen Verbindungen unterschiedlichster Art, die in geringer Menge im Hartsalz, das zur Herstellung der Ausgangssalzlösung verwendet wird, und im Wasser nach der Vorrichtung zur Wasserenthärtung mit lonenaustauschharzen enthalten sein können. In der Zeit zwischen den Reinigungsvorgängen des elektrochemischen Reaktors ist es erforderlich, die eingestellten Betriebsparameter des elektrochemischen Systems periodisch zu ändern, indem sie an die sich mit der Zeit verschlechternden Betriebsbedingungen wegen der Bildung von Ablagerungen im elektrochemischen Reaktor angepasst werden. Diese Vorgänge erfordern Zeit und die Aufmerksamkeit des Bedienungspersonals für sämtliche peripheren Vorrichtungen, die Bestandteile des einheitlichen technischen elektrochemischen Systems zur Synthese der Oxidationsmittellösung sind: für den Wasserenthärter, für die Vorrichtung zur Herstellung von Salzlösung und für die Reguliervorrichtungen. The device chosen as the prototype according to US Pat. No. 7,897,023 B2 is closest to the technical nature and the result to be achieved. This device represents an electrochemical system comprising a diaphragm electrolysis apparatus with a ceramic tubular ultrafiltration diaphragm, with a catholyte and anolyte circulation circuit with corresponding separating tanks for separating electrolysis gases and with heat exchanger devices for cooling the catholyte and anolyte Dosing pump with salt solution container existing device for supplying the cleaned salt solution under pressure into the anode compartment, a device for dissolving the moist gaseous products of the electrochemical anode reactions in the water stream to obtain the oxidizing agent solution, a device for overpressure stabilization in the anode compartment, a collecting container for the oxidizing agent solution and a device for the metered introduction of catholyte from the deposition container of the cathode circuit into the oxidizing agent solution to be synthesized. A disadvantage of this device is that multivalent ions, including heavy metal ions, are present in the finished product, ie in the solution of chlorine oxygen and hydroperoxide oxidants in water. These ions usually occur in drinking water or natural fresh water, which is used for the preparation of the starting salt solution and for the recovery of the oxidizing agent solution by dissolving the gaseous products of the electrochemical anode reactions in the fresh water stream, which contain microdrops of moisture with dissolved singlet oxygen, ozone and hydrogen peroxide . Multivalent metal ions, and especially heavy metal ions, are known to be catalysts for the chemical decomposition of active chlorine and active oxygen compounds - hypochlorous acid and hydrogen peroxide. For this reason, the oxidant solutions produced in this device lose their bioactivity within a few days due to the self-decomposition under the action of catalytically active ions. Another disadvantage of this technical solution is the necessary periodic cleaning of the electrode rooms of the electrochemical reactor from oxidized organic compounds of various kinds, which are contained in small amounts in the hard salt used to prepare the starting salt solution and in the water after the device for water softening with ion exchange resins can. In the period between the cleaning processes of the electrochemical reactor it is necessary to periodically change the set operating parameters of the electrochemical system by adapting them to the deteriorating operating conditions due to the formation of deposits in the electrochemical reactor. These operations require time and operator attention for all peripheral devices that are part of the unified technical electrochemical system for the synthesis of the oxidant solution: for the water softener, for the device for producing saline solution and for the regulating devices.
Aufgabe der Erfindung ist, die Zeit, über die die bioziden Eigenschaften des Endprodukts, der Oxidationsmittellösung, erhalten bleiben, durch die Reinigung des Wassers von Härtebildnern und multivalenten Metallioden sowie die Zeit für den kontinuierlichen bzw. wiederholt kurzzeitigen Betrieb des elektrochemischen Systems zwischen den Wartungsarbeitsgängen zu verlängern, ohne dass dessen Betriebsparameter durch die Reinigung der Salzlösung von organischen Beimischungen bei vollständiger Vermeidung des Verbrauchs an zusätzlichen chemischen Reagenzien korrigiert werden müssen. The object of the invention is to increase the time over which the biocidal properties of the end product, the oxidizing agent solution, are obtained by cleaning the water from hardening agents and multivalent metal diodes, and the time for the continuous or repeated short-term operation of the electrochemical system between the maintenance operations extend without having to correct its operating parameters by cleaning the salt solution from organic admixtures while completely avoiding the consumption of additional chemical reagents.
Das technische Ergebnis der Erfindung wird dadurch erreicht, dass im Unterschied zu der bekannten technischen Lösung beim Eintritt des Wassers in die Vorrichtung zur Mischung des Süßwasserstroms mit den gasförmigen Oxidationsmitteln ein Filter angeordnet ist, vor dem an der Zuführungsleitung für das Süßwasser eine Einrichtung zur dosierten Einbringung des Katholyts aus dem Abscheidebehälter des Kathodenkreises in den Wasserstrom montiert ist und das Salz in der Vorrichtung für die Zuführung der Salzlösung in den Anodenraum mittels Einrichtung zur dosierten Einbringung der Oxidationsmittellösung aus dem Sammelbehälter in den Behälter der Salzlösevorrichtung gelöst wird, an dessen Ausgang ein Filter angeordnet ist, der mit dem Eingang der Dosierpumpe für die Zuführung der Salzlösung unter Druck in den Anodenraum des Elektrolyseapparates verbunden ist. The technical result of the invention is achieved in that, in contrast to the known technical solution, when the water enters the device for mixing the fresh water stream with the gaseous oxidizing agents, a filter is arranged in front of which A supply line for the fresh water is a device for the metered introduction of the catholyte from the separating container of the cathode circuit into the water flow and the salt in the device for the supply of the salt solution into the anode compartment by means of the metered introduction of the oxidizing agent solution from the collecting container into the container of the salt dissolving device is solved, at the output of which a filter is arranged, which is connected to the input of the metering pump for supplying the salt solution under pressure into the anode compartment of the electrolysis apparatus.
In Fig. 1 ist das hydraulische Grundschaltbild des elektrochemischen Systems zur Synthese der Oxidationsmittellösung aus Alkalimetallchloriden, vorzugsweise Natriumchlorid, dargestellt. 1 shows the basic hydraulic circuit diagram of the electrochemical system for the synthesis of the oxidizing agent solution from alkali metal chlorides, preferably sodium chloride.
Das elektrochemische System beinhaltet einen Diaphragma-Elektrolyseapparat elektrochemischen Reaktor (1 ) mit koaxial angeordneten Elektroden - der Anode (2), der Kathode (3) und dem Diaphragma (4). Das verfahrenstechnische Schema der Anodensynthese der Oxidationsmittel besteht aus dem Anodenraum (5) des Reaktors (1 ), dessen Eingang über das Rückschlagventil (6) mit dem Ausgang der Flochdruck-Dosierpumpe (7) verbunden ist, deren Eingang ihrerseits mit dem Filter (8) verbunden ist, der mit dem Behälter zum Lösen des Salzes (9) verbunden ist, in dem die Ausgangssalzlösung hergestellt und gereinigt wird. Der Ausgang des Anodenraums (5) ist mit dem Abscheidebehälter (10) zur Trennung der gasförmigen Produkte der elektrochemischen Anodenreaktionen vom Anolyt verbunden. Der Ausgang im unteren Teil des Abscheidebehälters (10) ist mit dem Eingang des Anodenraums (5) des elektrochemischen Reaktors (1 ) verbunden, wobei dadurch der Anodenkreis des Anolyts geschlossen wird. Der Ausgang im oberen Teil des Abscheidebehälters (10) ist über das Rückschlagventil (11 ) mit der Vorrichtung (12) zum Lösen der gasförmigen Produkte der elektrochemischen Anoden-Reaktionen in Süßwasser verbunden. Der Ausgang der Vorrichtung (12) ist mit dem Vordruckregler (13) verbunden, der bei Betrieb des elektrochemischen Systems eine konstante Überschreitung des Drucks im Anodenkreis des elektrochemischen Reaktors (1 ) über den Druck im Kathodenkreis durch Aufbau eines geregelten vorgegebenen hydraulischen Widerstands im Oxidationsmittellösungsstrom sicherstellt. In der Hydraulikleitung, die den Ausgang der Vorrichtung (12) mit dem Vordruckregler (13) verbindet, ist ein Messfühler für das Leitfähigkeitsvermögen derThe electrochemical system includes a diaphragm electrolysis apparatus electrochemical reactor (1) with coaxially arranged electrodes - the anode (2), the cathode (3) and the diaphragm (4). The procedural scheme of the anode synthesis of the oxidizing agents consists of the anode compartment (5) of the reactor (1), the input of which is connected via the check valve (6) to the outlet of the flosh pressure metering pump (7), the input of which in turn is connected to the filter (8) connected to the container for dissolving the salt (9), in which the starting salt solution is prepared and purified. The outlet of the anode compartment (5) is connected to the separating container (10) for separating the gaseous products of the electrochemical anode reactions from the anolyte. The outlet in the lower part of the separating tank (10) is connected to the inlet of the anode compartment (5) of the electrochemical reactor (1), the anode circuit of the anolyte thereby being closed. The outlet in the upper part of the separating container (10) is connected via the check valve (11) to the device (12) for dissolving the gaseous products of the electrochemical anode reactions in fresh water. The output of the device (12) is connected to the upstream pressure regulator (13) which, when the electrochemical system is in operation, ensures that the pressure in the anode circuit of the electrochemical reactor (1) is constantly exceeded by the pressure in the cathode circuit by building up a regulated, predetermined hydraulic resistance in the oxidant solution stream . In the hydraulic line, which connects the outlet of the device (12) with the admission pressure regulator (13), there is a sensor for the conductivity of the
Oxidationsmittellösung„Xs“ angeordnet. Der Ausgang des Vordruckreglers (13) ist mit dem Eingang des Sammelbehälters für die Oxidationsmittellösung (14) verbunden, der mit Messfühlern für den zulässigen maximalen (15) und minimalen (16) Pegel der Oxidationsmittellösung ausgestattet ist. Oxidizing agent solution "X s " arranged. The output of the pre-pressure regulator (13) is connected to the input of the collecting container for the oxidizing agent solution (14), which is equipped with sensors for the permissible maximum (15) and minimum (16) level of the oxidizing agent solution.
Einer der Ausgänge des Sammelbehälters für die Oxidationsmittellösung (14) ist mit dem Eingang des Behälters (9) zur Herstellung und Reinigung der Salzlösung verbunden, der tiefer als der Sammelbehälter der Oxidationsmittellösung (14) liegt. Der andere Ausgang des Behälters (14) ist mit dem Eingang der Dosierpumpe (17) verbunden, die für die Zuführung der Oxidationsmittellösung zum Einsatzobjekt bestimmt ist, z. B. zum Punkt der Einbringung der Oxidationsmittel in das Wasserleitungssystem zur Keimfreimachung des Trinkwassers. One of the outputs of the collecting container for the oxidant solution (14) is with the entrance of the container (9) for producing and cleaning the saline solution, which is lower than the collecting container of the oxidizing agent solution (14). The other outlet of the container (14) is connected to the inlet of the metering pump (17), which is intended for the supply of the oxidizing agent solution to the application, for. B. at the point of incorporation of the oxidizing agent into the water supply system to sanitize the drinking water.
Das Wasser gelangt in die Vorrichtung (12) zum Lösen der gasförmigen Produkte der elektrochemischen Anodenreaktionen über das Rückschlagventil (18) und das Wärmetauschsystem des Anodenkreises des elektrochemischen Reaktors (1 ) vom Ausgang des Filters (19). In der hydraulischen Leitung, die den Ausgang des Wärmetauschsystems des Anodenkreises des elektrochemischen Reaktors (1 ) und den Eingang des Rückschlagventils (18) verbindet, ist ein Messfühler für das Leitfähigkeitsvermögen des Wassers„Xw“ angeordnet. An den Eingang des Filters (19) wird das durch die Wärmetauschvorrichtung (20) des Kathoden- Umlaufkreises gelaufene Wasser mit einem Zusatz von Katholyt aus dem Abscheideumlaufbehälter des Katholyts (21 ) zugeführt. Das Katholyt wird in den Wasserstrom am Ausgang aus der Wärmetauschvorrichtung des Kathoden-Umlaufkreises (20) mittels Dosierpumpe (22) eingebracht. In der hydraulischen Leitung, die den Ausgang des Wassers und den Eingang des Filters (19) verbindet, ist vor dem Punkt der Einbringung des Katholyts aus dem Abscheide-Umlaufbehälter des Katholyts (21 ) ein Messfühler für das Leitfähigkeitsvermögen des Ausgangswassers „X“ angeordnet. Außer der Wärmetauschvorrichtung (20) zur Kühlung des Katholyts und außer dem Abscheide-Umlaufbehälter des Katholyts (21 ) umfasst der Kathodenkreis des Katholyts den Kathodenraum (23) des elektrochemischen Reaktors (1 ), die Umlaufpumpe (24) und das Ventil (25) zur Befüllung des Abscheide-Umlaufbehälters des Katholyts (21 ) bei Inbetriebnahme des Systems und Zuspeisung von gereinigtem Wasser bei Betrieb des Systems. Der Abscheide-Umlaufbehälter des Katholyts (21 ) ist mit einer Abflussleitung des Katholyts versehen, das sich bei Betrieb des Systems bildet. Das Wasser wird dem elektrochemischen System für die Synthese der Oxidationsmittellösung aus dem Druckwasserleitungsnetz über den Grobfilter (Vorfilter) (26), das elektromagnetische Ventil (27) und den Nachdruckregler (28) zugeführt. The water enters the device (12) for dissolving the gaseous products of the electrochemical anode reactions via the check valve (18) and the heat exchange system of the anode circuit of the electrochemical reactor (1) from the outlet of the filter (19). In the hydraulic line, which connects the outlet of the heat exchange system of the anode circuit of the electrochemical reactor (1) and the inlet of the check valve (18), there is a sensor for the conductivity of the water "X w ". At the inlet of the filter (19), the water which has passed through the heat exchange device (20) of the cathode circulation circuit is fed with an addition of catholyte from the separation circulation container of the catholyte (21). The catholyte is introduced into the water flow at the outlet from the heat exchange device of the cathode circulation circuit (20) by means of a metering pump (22). In the hydraulic line, which connects the outlet of the water and the inlet of the filter (19), a sensor for the conductivity of the outlet water “X” is arranged before the point of introduction of the catholyte from the separating circulation container of the catholyte (21). In addition to the heat exchange device (20) for cooling the catholyte and the separating circulation container of the catholyte (21), the cathode circuit of the catholyte comprises the cathode chamber (23) of the electrochemical reactor (1), the circulation pump (24) and the valve (25) Filling the recycle circulation tank of the catholyte (21) when the system is started up and purified water is fed in when the system is in operation. The separating circulation tank of the catholyte (21) is provided with a drain line of the catholyte, which is formed during operation of the system. The water is fed to the electrochemical system for the synthesis of the oxidizing agent solution from the pressurized water supply network via the coarse filter (pre-filter) (26), the electromagnetic valve (27) and the secondary pressure regulator (28).
Das elektrochemische System zur Synthese der Oxidationsmittellösung funktioniert folgendermaßen. The electrochemical system for synthesizing the oxidant solution works as follows.
Bei der ersten Inbetriebnahme des elektrochemischen Systems (bei fehlendem Wasser und Lösungen im System) wird der Behälter (9) mit Hartsalz in der für die Synthese der vorgegebenen Menge Oxidationsmittellösung erforderlichen Menge im Verhältnis von Höchstverbrauch von 0,8 Gramm Salz pro 1 Liter Oxidationsmittellösung befüllt. Z. B. ist für die Herstellung von 25.000 Liter Oxidationsmittellösung mit einer Konzentration von aktiven Stoffen (Chlorsauerstoff- und Hydroperoxid-Verbindungen) von 500 mg/l der Behälter (9) mit 20 Kilogramm Salz zu befüllen. Der Behälter (9) wird mit gereinigtem und enthärtetem Wasser befüllt, wobei das Salz vollständig mit Wasser bedeckt sein muss. Dies erfolgt einmalig, bei der ersten Inbetriebnahme des Systems. Der Stutzen für die Wasserzuführung am Eingang des mechanischen Filters (26) wird mit der Druckleitung für das Süßwasser (Trinkwasser) verbunden. Mittels eines gesonderten Schalters wird das normal geschlossene elektromagnetische Ventil (27) mit Spannung beaufschlagt. Der vorgegebene Volumendurchstrom des Wassers durch das System sowie der vorgegebene Druck im Anodenkreis werden durch einen Nachdruckregler (28) und einen Vordruckregler (13) eingestellt, indem man sich nach den Anzeigewerten des Manometers M und des externen Durchflussmengenmessers (auf der Zeichnung nicht dargestellt) richtet. When the electrochemical system is started up for the first time (in the absence of water and solutions in the system), the container (9) with hard salt is added in the amount required for the synthesis of the specified amount of oxidizing agent solution in a ratio of maximum consumption of 0.8 Grams of salt filled per 1 liter of oxidizing agent solution. For example, for the production of 25,000 liters of oxidizing agent solution with a concentration of active substances (chlorine oxygen and hydroperoxide compounds) of 500 mg / l, the container (9) must be filled with 20 kilograms of salt. The container (9) is filled with purified and softened water, the salt having to be completely covered with water. This is done once, when the system is started up for the first time. The connection for the water supply at the entrance of the mechanical filter (26) is connected to the pressure line for the fresh water (drinking water). The normally closed electromagnetic valve (27) is supplied with voltage by means of a separate switch. The specified volume flow of water through the system and the specified pressure in the anode circuit are set by a secondary pressure regulator (28) and a pre-pressure regulator (13), based on the display values of the pressure gauge M and the external flow meter (not shown on the drawing) .
Mittels des Ventils (25) wir der Abscheidebehälter des Katholyts (21 ) mit Wasser befüllt, bis der Wasserstrahl aus der Abflussleitung des Abscheidebehälters (21 ) tritt, anschließend wird das Ventil in eine Stellung gebracht, die sicherstellt, dass Wasser in den Abscheideumlaufbehälter für das Katholyt (21 ) mit einer Geschwindigkeit von 20 - 30 Tropfen pro Minute zugeführt wird (wird anhand der Geschwindigkeit des Tropfenschlags aus der Abflussleitung des Abscheidebehälters für das Katholyt (21 ) bestimmt). Die Dosierpumpe (7) wird eingeschaltet und der Anodenraum (5) des elektrochemischen Reaktors (1 ) mit Salzlösung aus dem Behälter (9) befüllt. Das Ende des Befüllungsprozesses wird anhand der Erhöhung der Messfühlerwerte für dasBy means of the valve (25) we fill the separating tank of the catholyte (21) with water until the water jet comes out of the drain line of the separating tank (21), then the valve is brought into a position which ensures that water enters the separating circulation tank for the Catholyte (21) is fed at a rate of 20-30 drops per minute (is determined on the basis of the speed of the drop of the drop from the drain line of the separating container for the catholyte (21)). The metering pump (7) is switched on and the anode compartment (5) of the electrochemical reactor (1) is filled with salt solution from the container (9). The end of the filling process is determined by increasing the sensor values for the
Leitfähigkeitsvermögen der Oxidationsmittellösung„Xs“ ungefähr um das Doppelte gegenüber denConductivity of the oxidizing agent solution "X s " is approximately twice that of
Werten des Messfühlers für das Leitfähigkeitsvermögen des Wassers „Xw“ festgestellt. Die Steuerung der elektrischen Vorrichtungen des Systems (Pumpen, Stromquelle des elektrochemischen Reaktors) wird auf den Automatikblock (auf der Zeichnung nicht dargestellt), der mit den Messfühlern für den Pegel der Oxidationsmittellösung im Sammelbehälter (14) und denValues of the sensor for the conductivity of the water "X w " determined. The control of the electrical devices of the system (pumps, power source of the electrochemical reactor) is based on the automatic block (not shown in the drawing), which with the sensors for the level of the oxidizing agent solution in the collecting container (14) and
Messfühlern für das Leitfähigkeitsvermögen des konditionierten enthärteten Wasser „Xw“, derSensors for the conductivity of the conditioned softened water "X w ", the
Oxidationsmittellösung„Xs“ und des Ausgangswassers„X“ verbunden ist, umgestellt. Bei einem Pegel der Oxidationsmittellösung im Sammelbehälter (14) unter dem Messfühler (16) bzw. zwischen den Messfühlern (16) und (17) werden die Stromquelle des elektrochemischen Reaktors (auf der Zeichnung nicht dargestellt), die Katholyt-Umlaufpumpe (24), die Pumpe (22) für die dosierte Einbringung des Katholyts in den Süßwasserstrom und die Dosierpumpe (7) für die Zuführung der Salzlösung in den Anodenraum (5) des elektrochemischen Reaktors (1 ) eingeschaltet. Der Automatikblock, der die elektrischen Vorrichtungen des elektrochemischen Systems steuert, stellt die Regelung der Geschwindigkeit für die Zuführung des Katholyts mittels der Dosierpumpe (22) in das Ausgangssüßwasser auf der Grundlage der Signale der Messfühler für das Leitfähigkeitsvermögen des Wassers„Xw“ L“ sicher, indem das Leitfähigkeitsvermögen des Wassers nach dem Filter (19) aufrechterhalten wird, das vom Messfühler für das Leitfähigkeitsvermögen„Xw“ auf dem vorgegebenen Wert des Messbereichs festzuhalten ist, der durch das Verhältnis Xw = (1 ,0 ... 1 ,5) X' bestimmt wird. Der Automatikblock stellt ebenfalls die Regelung der Geschwindigkeit der Zuführung der Salzlösung mittels der Dosierpumpe (7) in den Anodenraum (5) des elektrochemischen Reaktors (1 ) auf der Grundlage der Signale der Messfühler für das Leitfähigkeitsvermögen„Xw“ und„Xs“ sicher, indem das Leitfähigkeitsvermögen der Oxidationsmittellösung„Xs“ auf dem vorgegebenen Wert des Messbereichs aufrechterhalten wird, der durch das Verhältnis Xs = (1 ,5 ... 2,5) Xw bestimmt wird. Oxidizing agent solution "X s " and the source water "X" is connected. At a level of the oxidizing agent solution in the collecting container (14) under the measuring sensor (16) or between the measuring sensors (16) and (17) the current source of the electrochemical reactor (not shown on the drawing), the catholyte circulation pump (24), the pump (22) for the metered introduction of the catholyte into the fresh water stream and the metering pump (7) for the supply of the salt solution into the anode compartment (5) of the electrochemical reactor (1). The automatic block, which controls the electrical devices of the electrochemical system, regulates the speed for the supply of the catholyte of the metering pump (22) into the output fresh water based on the signals from the water conductivity sensors "X w " L "by maintaining the water conductivity after the filter (19) determined by the conductivity sensor" X w ”is to be kept at the specified value of the measuring range, which is determined by the ratio X w = (1, 0 ... 1, 5) X '. The automatic block also ensures the regulation of the speed of the supply of the salt solution by means of the metering pump (7) into the anode compartment (5) of the electrochemical reactor (1) on the basis of the signals from the sensors for the conductivity "X w " and "X s " by maintaining the conductivity of the oxidizing agent solution "X s " at the specified value of the measuring range, which is determined by the ratio X s = (1, 5 ... 2.5) X w .
Bei Betrieb der Anlage im elektrochemischen Reaktor (1 ) laufen folgende Reaktionen ab. The following reactions occur when the system is operated in the electrochemical reactor (1).
Im elektrochemischen Reaktor (1 ) ist die Hauptreaktion die Freisetzung von molekularem Chlor im Anodenraum (5) und die Bildung von Natriumhydroxid im Kathodenraum (23): The main reaction in the electrochemical reactor (1) is the release of molecular chlorine in the anode compartment (5) and the formation of sodium hydroxide in the cathode compartment (23):
NaCI + H20 - e -> NaOH + 0,5 H2 + 0,5 Cl2. NaCI + H 2 0 - e -> NaOH + 0.5 H 2 + 0.5 Cl 2 .
Zugleich läuft im Anodenraum mit geringerer Stromausbeute die Synthese des Chlordioxids direkt aus der Salzlösung sowie aus der Salzsäure ab, die sich beim Lösen des molekularen Chlors in Anodennähe
Figure imgf000008_0001
bildet:
At the same time, the chlorine dioxide is synthesized directly from the salt solution and from the hydrochloric acid in the anode compartment with a lower current yield, which occurs when the molecular chlorine is dissolved near the anode
Figure imgf000008_0001
forms:
2NaCI + 6H20 - 10e -> 2CI02 + 2NaOH + 5 H2; 2NaCI + 6H 2 0 - 10e -> 2CI0 2 + 2NaOH + 5 H 2 ;
HCl + 2H20 - 5e -> CI02 + 5 H\ HCl + 2H 2 0 - 5e -> CI0 2 + 5 H \
Im Anodenraum des Reaktors bildet sich Ozon durch direkte Wasserzersetzung und durch Oxidation des freiwerdenden Sauerstoffs: Ozone forms in the anode compartment of the reactor through direct water decomposition and through oxidation of the released oxygen:
3H20 - 6e 03 + 6H ' ; 2H20 - 4e -> 4H + 02; =^ 02 + H20 - 2e -> 03 + 2 H\ 3H 2 0 - 6e 0 3 + 6H ' ; 2H 2 0 - 4e -> 4H ' + 0 2 ; = ^ 0 2 + H 2 0 - 2e -> 0 3 + 2 H \
Mit einer geringen Stromausbeute verläuft die Bildungsreaktion von aktivenThe formation reaction of active ones takes place with a low current yield
Sauerstoffverbindungen: Oxygen compounds:
H20 - 2e -> 2H' + 0'; H20 - e -> HO‘ + H'; 2H20 - 3e -> H02 + 3H'. H 2 0 - 2e -> 2H ' + 0 ' ; H 2 0 - e -> HO '+ H ' ; 2H 2 0 - 3e -> H0 2 + 3H ' .
Die Stromausbeute für die Bildung von Chlordioxid, Ozon, Singulett-Sauerstoff undThe current efficiency for the formation of chlorine dioxide, ozone, singlet oxygen and
Wasserstoffperoxid erhöht sich bei Verringerung des Mineralgehalts der wässrigen Natriumchlorid- Ausgangslösung und erreicht 20 - 30 % bei einer Salzkonzentration in der Ausgangslösung im Bereich 80 - 150 g/l bei einer Anodendichte von fünf- bis siebentausend Ampere pro Quadratmeter (5000 - 7000 A/m2). Bei Erhöhung des Salzgehalts in der Ausgangslösung auf 250 - 300 g/l verringert sich die Stromausbeute der Bildungsreaktionen von Chlordioxid, Ozon, Singulett- Sauerstoff und Wasserstoffperoxid auf 1 - 2 % bei einer Anodendichte von 5000 - 7000 A/m2 und auf 0, 1 - 0,2 % bei einer Anodendichte von 2000 - 3000 A/m2. Hydrogen peroxide increases with a decrease in the mineral content of the aqueous sodium chloride starting solution and reaches 20-30% with a salt concentration in the starting solution Range 80 - 150 g / l with an anode density of five to seven thousand amperes per square meter (5000 - 7000 A / m 2 ). Increasing the salt content in the starting solution to 250-300 g / l reduces the current efficiency of the formation reactions of chlorine dioxide, ozone, singlet oxygen and hydrogen peroxide to 1-2% with an anode density of 5000-7000 A / m 2 and to 0. 1 - 0.2% with an anode density of 2000 - 3000 A / m 2 .
Beim Lösen des gasförmigen Produkts der Anodisierung der Natriumchloridlösung in Wasser verläuft in der Regel eine Reaktion, die mit folgender Gleichung ausgedrückt wird: When the gaseous product of the anodization of the sodium chloride solution is dissolved in water, there is usually a reaction which is expressed by the following equation:
Cl2 + H20 «-> HOCI + HCL Cl 2 + H 2 0 «-> HOCI + HCL
Bekanntlich ist hypochlorige Säure, deren Mengengehalt in der Lösung durch den sinkenden pH- Wert infolge der Bildung von Salzsäure beschränkt ist, ein elementares antimikrobielles Mittel. Der pH-Wert kann durch Einbringung von Alkalilauge, d. h. z. B. Natriumhydroxid, verändert werden. Allerdings führt dies zur Bildung von unerwünschten (Natriumchlorid) und wenig reaktionsfähigen (Natriumhypochlorit) Produkten. Das Natriumhypochlorit als Salz einer schwachen Säure (hypochlorige Säure) und einer starken Base (Natriumhydroxid) verfügt über eine um das 250- bis 350-Fache verringerte antimikrobielle Aktivität im Vergleich zur hypochlorigen Säure. It is known that hypochlorous acid, the amount of which in the solution is limited by the falling pH due to the formation of hydrochloric acid, is an elementary antimicrobial agent. The pH value can be adjusted by adding alkali lye, i.e. H. e.g. As sodium hydroxide can be changed. However, this leads to the formation of undesirable (sodium chloride) and less reactive (sodium hypochlorite) products. The sodium hypochlorite as a salt of a weak acid (hypochlorous acid) and a strong base (sodium hydroxide) has a 250 to 350 times reduced antimicrobial activity compared to hypochlorous acid.
HOCI + HCl + 2NaOH -> NaOCI + NaCI + H20. HOCI + HCl + 2NaOH -> NaOCI + NaCI + H 2 0.
Die Bildung von Natriumhypochlorit kann bei gleichzeitiger Erhöhung des pH-Wertes der Oxidationsmittellösung mit gleichzeitiger Erhöhung der Konzentration der hypochlorigen Säure und Entfernung der Härtebildner und der multivalenten Metallionen, u. a. des Eisens, durch Einbringung von freie Hydroxygruppen enthaltendem Katholyt in den Wasserstrom vermieden werden. The formation of sodium hypochlorite can be accompanied by a simultaneous increase in the pH of the oxidizing agent solution with a simultaneous increase in the concentration of the hypochlorous acid and removal of the hardening agents and the multivalent metal ions, and the like. a. of iron can be avoided by introducing catholyte containing free hydroxyl groups into the water flow.
Bekanntlich hat der Katholyt eine außerordentlich hohe chemische Adsorptionsaktivität in Hydratbildungsreaktionen. Die erhöhte Reaktionsfähigkeit des Katholyts erklärt sich unter anderem durch die im Katholyt enthaltene große Menge an freien Hydroxy-Gruppen und gelöstem Wasserstoff. As is known, the catholyte has an extremely high chemical adsorption activity in hydrate formation reactions. The increased reactivity of the catholyte is explained, among other things, by the large amount of free hydroxyl groups and dissolved hydrogen contained in the catholyte.
Bei der wechselseitigen Beeinflussung von Katholyt und im Wasser enthaltenen Elektrolyten erfolgt die Bildung von in Wasser unlöslichen Verbindungen: The mutual influence of catholyte and electrolytes contained in water leads to the formation of water-insoluble compounds:
Figure imgf000009_0001
Figure imgf000010_0001
Figure imgf000009_0001
Figure imgf000010_0001
Am Filter (19) werden die Hydroxide und die gebildeten Flocken - die Teilchenaggregate der Hydroxide mit den adsorbierten Molekülen organischer Verbindungen, die mikrokolloiden Teilchen und Wasserstoffbläschen abgeschieden und das von multivalenten Metallkationen gereinigte und enthärtete Wasser, das geringe Konzentrationen an gelöstem Wasserstoff und freie Hydroxygruppen enthält, strömt in die Vorrichtung zum Lösen der Oxidationsmittel (12) ein, diese bewirken eine Erhöhung der Konzentration an hypochloriger Säure in der Oxidationsmittellösung entsprechend der folgenden Reaktion: Cl2 + H20 + OH- -> 2HOCI. The hydroxides and the flakes formed - the particle aggregates of the hydroxides with the adsorbed molecules of organic compounds, the microcolloid particles and hydrogen bubbles and the water which has been purified and freed from multivalent metal cations and which contains low concentrations of dissolved hydrogen and free hydroxyl groups, are separated off on the filter (19) , flows into the device for dissolving the oxidizing agents (12), these cause an increase in the concentration of hypochlorous acid in the oxidizing agent solution in accordance with the following reaction: Cl 2 + H 2 0 + OH- -> 2HOCI.
Die Oxidationsmittellösung wird je nach gesammelter Menge im Behälter (14) des elektrochemischen Systems außer für ihre Hauptbestimmung ebenfalls in geringen Mengen als Agens für das Lösen des Salzes im Behälter (9) verwendet, was die organischen Beimischungen oxidativ zersetzt, die ursprünglich im Steinsalz enthalten und bei herkömmlichen Verfahren der Herstellung von Salz für den Haushaltsbedarf und zahlreichen industriellen Anwendungen schwer zu entfernen sind. Die oxydierten und koagulierten organischen Fremdverbindungen werden vom Filter (8) am Ausgang des Behälters (9) zurückgehalten. Das Lösen der Salze durch die Oxidationsmittellösung ermöglicht es, die mikrobiologische Reinheit des Mittels im Salzlösebehälter zu gewährleisten. Dadurch muss er nicht mehr regelmäßig bis zum Ende des Prozesses des Lösens der gesamten befüllten Salzmenge gewartet werden. Vor der Zuführung in den Anodenraum des elektrochemischen Reaktors ist es nicht erforderlich, aus der Salzlösung die multivalenten Metallionen, u. a. auch Schwermetallionen, zu entfernen. Sämtliche Metallkationen, die in den Anodenraum als Teil der Salzlösung unter der Einwirkung des Druckgefälles und des elektrischen Feldes gelangen, werden zusammen mit dem Flüssigkeitsfilterstrom in den Kathodenraum über das poröse UV-Medium des keramischen Diaphragmas entfernt. Im Kathodenraum werden die multivalenten Metallkationen in Hydroxide umgewandelt und aus dem System über die Abflussleitung aus dem Abscheideumlaufbehälter des Katholyts (21 ) entfernt. Depending on the amount collected in the container (14) of the electrochemical system, the oxidizing agent solution is also used, in addition to its main purpose, in small quantities as an agent for dissolving the salt in the container (9), which oxidatively decomposes the organic admixtures that originally contained in the rock salt and are difficult to remove in conventional domestic salt manufacturing processes and numerous industrial applications. The oxidized and coagulated organic foreign compounds are retained by the filter (8) at the outlet of the container (9). The dissolution of the salts by the oxidizing agent solution makes it possible to ensure the microbiological purity of the agent in the salt dissolving tank. As a result, it no longer has to be regularly waited until the end of the process of dissolving the entire filled amount of salt. Before being fed into the anode compartment of the electrochemical reactor, it is not necessary to remove the multivalent metal ions, etc. from the salt solution. a. also remove heavy metal ions. All metal cations that enter the anode compartment as part of the salt solution under the influence of the pressure drop and the electric field are removed together with the liquid filter stream into the cathode compartment via the porous UV medium of the ceramic diaphragm. In the cathode compartment, the multivalent metal cations are converted into hydroxides and removed from the system via the drain line from the deposition circulation container of the catholyte (21).
Die Versuche mit dem elektrochemischen System wurden im Vergleich mit dem Prototyp der Vorrichtung, der nach dem Patent US 7 897 023 B2 ausgeführt und mit einem Ionenaustauscher (Wasserenthärter) und mit einem Behälter zum Lösen des Salzes und zur Herstellung einer Salzlösung ergänzt wurde, durchgeführt. Für eine präzisere Vergleichsanalyse wurde das Wasser aus dem lonenaustausch-Enthärter nicht nur zur Herstellung der Salzlösung, sondern auch zum Lösen der gasförmigen Produkte des Anodenraums des elektrochemischen Reaktors verwendet. Der lonenaustausch-Enthärter wurde an die Trinkwasser-Druckleitung angeschlossen. Die Vorrichtung gemäß Patent der USA wurde ebenfalls mit einem Sammelbehälter für die Oxidationsmittellösung ergänzt. Beide vergleichbaren Systeme enthielten einen elektrochemischen Reaktor, der aus vier elektrochemischen modularen Elementen (Zellen) gemäß Patent EP 0 842 122 B1 bestand. Die wässrige Ausgangssalzlösung enthielt 250 g/l Natriumchlorid, der Gehalt an Härtebildnern in der Ausgangslösung betrug 0,3 MG-QKB/P (1 da entspricht 0,3566 MG-QKB/P im elektrochemischen System gemäß Patent US 7 897 023 B2 und 4,5 MG-QKB/P im Behälter (9) des Systems gemäß der neuen technischen Lösung. Der Grund für den Unterschied war der geringe Gehalt an Härtebildnern im Wasser nach dem lonenaustausch-Enthärter und der bedeutend höhere Gehalt an Härtebildnern im herkömmlichen Leitungstrinkwasser, aus dem ursprünglich die Ausgangssalzlösung im elektrochemischen System gemäß der neuen technischen Lösung hergestellt wurde. Die Stromstärke durch den elektrochemischen Reaktor in der Prototyp- Vorrichtung betrug 40 Ampere bei einer Spannung von 5 Volt. Die gleichen Werte wurden für den elektrochemischen Reaktor im elektrochemischen System gemäß der neuen technischen Lösung eingestellt. Demgemäß wurden in jedem Vergleichssystem 52 g/h Oxidationsmittel hergestellt. Die Oxidationsmittellösung, die im Prototyp-System mit einer Geschwindigkeit von 100 l/h hergestellt wurde, hatte eine Oxidationsmittelkonzentration von 500 mg/l, einen pH-Wert von 2,8 und einen Gesamtmineralgehalt von 0,86 g/l. Der Gehalt an Härtebildnern in der Oxidationsmittellösung betrug 0,2 MG-QKB/P. Bei einer dosierten Einbringung des Katholyts, das sich bei der Synthese der Oxidationsmittellösung bildet, erhöhte sich der pH-Wert der Lösung am Ausgang auf 6,0 bei gleichzeitiger Erhöhung des Mineralgehalts der Lösung auf 1 ,5 g/l. Die Oxidationsmittellösung, die mit einer Geschwindigkeit von 100 l/h in der Vorrichtung gemäß der neuen technischen Lösung hergestellt wird, hatte einen pH-Wert von 3,0 bei einer Oxidationsmittelkonzentration von 500 mg/l und einem Gesamtmineralgehalt von 0,66 g/l. Bei der dosierten Einbringung von Katholyt in das Ausgangswasser erhöhte sich der pH-Wert der Oxidationsmittellösung bei gleichzeitiger Erhöhung des Mineralgehalts auf 0,82 g/l. Die Härte der Oxidationsmittellösung lag im Bereich 0,8 MG-QKB/P, verringerte sich allerdings im Verlauf von 2 Stunden Betrieb auf 0,6 MG-QKB/P. Die Auswertung der Ergebnisse dieser Untersuchungen zeigt, dass die Einbringung von Katholyt vor dem Filter (19) die Härte des Wassers zum Lösen der gasförmigen Produkte der Anodisierung der Natriumchloridlösung wesentlich verringert und dass die Einbringung der Oxidationsmittellösung mit einem reduzierten Gehalt an Härtebildnern im Behälter (9) zur Herstellung der Salzlösung den Gehalt an Härtebildnern in der Oxidationsmittellösung wesentlich verringert. The tests with the electrochemical system were carried out in comparison with the prototype of the device, which was carried out according to US Pat. No. 7,897,023 B2 and was supplemented with an ion exchanger (water softener) and with a container for dissolving the salt and for producing a saline solution. For a more precise comparative analysis, the water from the ion exchange softener was used not only to produce the salt solution, but also to dissolve the gaseous products of the anode compartment of the electrochemical reactor. The ion exchange softener was connected to the drinking water pressure line. The The device according to the US patent was also supplemented with a collecting container for the oxidizing agent solution. Both comparable systems contained an electrochemical reactor which consisted of four electrochemical modular elements (cells) according to patent EP 0 842 122 B1. The aqueous starting salt solution contained 250 g / l sodium chloride, the hardness content in the starting solution was 0.3 MG-QKB / P (1 da corresponds to 0.3566 MG-QKB / P in the electrochemical system according to US Pat. No. 7,897,023 B2 and 4 , 5 MG-QKB / P in the tank (9) of the system according to the new technical solution The reason for the difference was the low level of hardness in water after the ion exchange softener and the significantly higher level of hardness in conventional tap drinking water which originally produced the starting salt solution in the electrochemical system according to the new technical solution. The current through the electrochemical reactor in the prototype device was 40 amperes at a voltage of 5 volts. The same values were used for the electrochemical reactor in the electrochemical system according to the new Accordingly, 52 g / h of oxidizing agents were produced in each comparison system The oxidant solution, which was produced in the prototype system at a speed of 100 l / h, had an oxidant concentration of 500 mg / l, a pH of 2.8 and a total mineral content of 0.86 g / l. The hardness-forming agent content in the oxidizing agent solution was 0.2 MG-QKB / P. With a metered introduction of the catholyte, which is formed during the synthesis of the oxidizing agent solution, the pH value of the solution at the outlet increased to 6.0, while the mineral content of the solution was increased to 1.5 g / l. The oxidant solution, which is produced at a rate of 100 l / h in the device according to the new technical solution, had a pH of 3.0 at an oxidant concentration of 500 mg / l and a total mineral content of 0.66 g / l . With the metered introduction of catholyte into the initial water, the pH value of the oxidizing agent solution increased while the mineral content increased to 0.82 g / l. The hardness of the oxidizing agent solution was in the range of 0.8 MG-QKB / P, but decreased to 0.6 MG-QKB / P in the course of 2 hours of operation. The evaluation of the results of these investigations shows that the introduction of catholyte in front of the filter (19) significantly reduces the hardness of the water for dissolving the gaseous products of the anodization of the sodium chloride solution and that the introduction of the oxidizing agent solution with a reduced content of hardening agents in the container (9 ) for the production of the salt solution, the content of hardness in the oxidizing agent solution is significantly reduced.
Beide Systeme liefen kontinuierlich je 10 Stunden täglich über 10 Tage. Proben der Oxidationsmittellösungen wurden zwei Mal entnommen: am Ende des zweiten Tages des Betriebs vergleichbarer elektrochemischer Systeme (20 Betriebsstunden) und nach 10 Tagen (100 Betriebsstunden). Die Lösung aus dem Prototyp-System wies nach zwanzig Betriebsstunden des Systems folgende Werte auf: pH-Wert 6,4; Oxidationsmittelkonzentration 480 mg/l; Mineralgehalt 1 ,4 g/l. Nach zehn Tagen verringerte sich die Oxidationsmittelkonzentration in der entnommenen Probe (Menge der Lösung 1 Liter) auf 460 mg/l. Der Gehalt an Härtebildnern in der Oxidationsmittellösung des Prototyps betrug 0,9 MG-QKB/P, d. h. es war eine Verschlechterung in der Funktionsweise des Ionenaustauschfilters festzustellen. Die Lösung aus dem System gemäß der neuen technischen Lösung wies nach 20 Betriebsstunden des Systems folgende Werte auf: pH- Wert 5,9; Oxidationsmittelkonzentration 510 mg/l; Gesamtmineralgehalt 0,83 g/l. Nach 10 Tagen war die Oxidationsmittelkonzentration in der entnommenen Probe (Lösungsprobe) unverändert. Der Gehalt an Härtebildnern in der Oxidationsmittellösung des Prototyps betrug 0,6 MG-QKB/P, d. h. die Einbringung von Katholyt in das Ausgangswasser vor dem Filter ermöglichte eine Reinigung des Wassers von Härtebildnern. Damit blieben die Oxidationsmittel in der Lösung länger erhalten. Both systems ran continuously for 10 hours a day for 10 days. Samples of the oxidant solutions were taken twice: at the end of the second day of operating comparable electrochemical systems (20 hours of operation) and after 10 days (100 hours of operation). The solution from the prototype system showed after twenty hours of operation Systems the following values: pH 6.4; Oxidant concentration 480 mg / l; Mineral content 1.4 g / l. After ten days, the oxidant concentration in the sample taken (amount of the solution 1 liter) decreased to 460 mg / l. The hardness content in the oxidant solution of the prototype was 0.9 MG-QKB / P, ie a deterioration in the functioning of the ion exchange filter was observed. The solution from the system according to the new technical solution had the following values after 20 hours of operation of the system: pH 5.9; Oxidizer concentration 510 mg / l; Total mineral content 0.83 g / l. After 10 days, the oxidant concentration in the sample (solution sample) taken was unchanged. The hardness content in the oxidant solution of the prototype was 0.6 MG-QKB / P, ie the introduction of catholyte into the starting water in front of the filter made it possible to purify the water from hardness builders. As a result, the oxidizing agents remained in the solution for longer.
Die Lösung aus dem Prototyp-System wies nach einhundert Betriebsstunden des Systems folgende Werte auf: pH-Wert 6,3; Oxidationsmittelkonzentration 470 mg/l; Gesamtmineralgehalt 1 ,4 g/l. Nach 10 Tagen verringerte sich die Oxidationsmittelkonzentration in der entnommenen Probe (Menge der Lösung 1 Liter) auf 440 mg/l. Der Gehalt an Härtebildnern in der Oxidationsmittellösung des Prototyps betrug 3,8 MG-QKB/P, was offensichtlich mit der signifikanten Verschlechterung der Funktion des Ionenaustauschfilters im Zusammenhang steht. Die Lösung aus dem System gemäß der neuen technischen Lösung wies nach einhundert Betriebsstunden folgende Werte auf: Werte: pH-Wert 5,9; Oxidationsmittelkonzentration 500 mg/l; Gesamtmineralgehalt 0,83 g/l. Nach 10 Tagen Betrieb war die Oxidationsmittelkonzentration in der entnommenen Probe (Lösungsprobe) unverändert. Der Gehalt an Härtebildnern in der Oxidationsmittellösung aus dem System gemäß der neuen technischen Lösung betrug 0,6 MG- QKB/P, d. h. die Einbringung von Katholyt in das Ausgangswasser vor dem Filter ermöglichte es, das Wassers effektiv und über längere Zeit von Härtebildnern zu reinigen. Dadurch blieben die Oxidationsmittel in der Lösung länger erhalten. Eine Prüfung der Behälter für die Lösung des Salzes und die Herstellung der Salzlösung zeigte einen Biofilm an Mikroorganismen im Behälter des Prototyp-Systems. Im Behälter (9) des Systems gemäß der neuen technischen Lösung fehlte der Biofilm vollständig. Diese Tatsache ist äußerst wichtig, da die organischen Stoffe, die sich bei der Tätigkeit des Biofilms bilden, bei deren Oxydation im Anodenraum des elektrochemischen Reaktors in der Lage sind, die elektrolytische Zersetzung des Natriumchlorids durch die Bildung schwer zu entfernender Verunreinigungen an den Elektroden und am Diaphragma (Membran) negativ zu beeinflussen. Bezugszeichen The solution from the prototype system showed the following values after one hundred hours of operation of the system: pH 6.3; Oxidant concentration 470 mg / l; Total mineral content 1.4 g / l. After 10 days, the oxidant concentration in the sample taken (amount of the solution 1 liter) decreased to 440 mg / l. The hardness level in the prototype's oxidant solution was 3.8 MG-QKB / P, which is obviously related to the significant deterioration in the function of the ion exchange filter. The solution from the system according to the new technical solution had the following values after one hundred hours of operation: Values: pH 5.9; Oxidizing agent concentration 500 mg / l; Total mineral content 0.83 g / l. After 10 days of operation, the oxidant concentration in the sample taken (solution sample) was unchanged. The content of hardening agents in the oxidizing agent solution from the system according to the new technical solution was 0.6 MG-QKB / P, ie the introduction of catholyte into the starting water before the filter made it possible to purify the water effectively from hardening agents over a long period of time . This kept the oxidizing agents in the solution longer. Examination of the containers for the solution of the salt and the production of the salt solution showed a biofilm of microorganisms in the container of the prototype system. The biofilm was completely missing in the container (9) of the system according to the new technical solution. This fact is extremely important, since the organic substances that form during the operation of the biofilm, when oxidized in the anode compartment of the electrochemical reactor, are able to cause the electrolytic decomposition of the sodium chloride by the formation of impurities on the electrodes and on which are difficult to remove To influence the diaphragm (membrane) negatively. Reference numerals
1 Reaktor 1 reactor
2 Anode  2 anode
3 Kathode  3 cathode
4 Diaphragma  4 diaphragm
5 Anodenraum  5 anode compartment
6 Rückschlagventil  6 check valve
7 Hochdruck-Dosierpumpe  7 High pressure metering pump
8 Filter  8 filters
9 Salz  9 salt
10 Abscheidebehälter  10 separation tanks
1 1 Rückschlagventil  1 1 check valve
12 Vorrichtung  12 device
13 Vordruckregler  13 pre-pressure regulator
14 Oxidationsmittellösung  14 Oxidizer solution
15 maximaler Pegel  15 maximum level
16 minimaler Pegel  16 minimum levels
17 Dosierpumpe  17 dosing pump
18 Rückschlagventil  18 check valve
19 Eingang Filter  19 Filter input
20 Wärmetauschvorrichtung  20 heat exchange device
21 Katholyt  21 catholyte
22 Dosierpumpe  22 dosing pump
23 Kathodenraum  23 cathode compartment
24 Umlaufpumpe  24 circulation pump
25 Ventil  25 valve
26 Grobfilter (Vorfilter)  26 coarse filter (pre-filter)
27 elektromagnetisches Ventil  27 electromagnetic valve
28 Nachdruckregler  28 pressure regulator

Claims

Patentanspruch  Claim
Elektrochemisches System zur Synthese einer Oxidationsmittellösung aus Wasser und einer Natriumchloridlösung, das einen Diaphragma-Elektrolyseapparat (4) mit einem röhrenförmigen keramischen Ultrafiltrationsdiaphragma (4), einem Umlaufkreis des Katholyts und Anolyts, mit entsprechenden Abscheidebehältern (10, 21 ) zur Trennung der Elektrolysegase sowie mit Wärmetauschervorrichtungen (20) zur Kühlung des Katholyts und Anolyts, eine Vorrichtung für die Zuführung von wässriger Salzlösung in einen Anodenraum (5) des Diaphragma- Elektrolyseapparats (4) unter Druck, die aus einer Dosierpumpe (7) mit einem Behälter (9) zum Lösen des Salzes besteht, eine Vorrichtung zum Lösen feuchter gasförmiger Produkte der elektrochemischen Anodenreaktionen im Süßwasserstrom zur Gewinnung einer Oxidationsmittellösung, eine Vorrichtung zur Stabilisierung des Überdrucks im Anodenraum (5), einen Sammelbehälter (14) für die Oxidationsmittellösung sowie eine Einrichtung für die dosierte Zuführung des Katholyts aus dem Abscheidebehälter (21 ) des Kathodenkreises in die zu synthetisierende Oxidationsmittellösung umfasst, dadurch gekennzeichnet, dass Electrochemical system for the synthesis of an oxidizing agent solution from water and a sodium chloride solution, which comprises a diaphragm electrolysis apparatus (4) with a tubular ceramic ultrafiltration diaphragm (4), a circulation circuit of the catholyte and anolyte, with corresponding separating containers (10, 21) for separating the electrolysis gases and with Heat exchanger devices (20) for cooling the catholyte and anolyte, a device for supplying aqueous salt solution into an anode space (5) of the diaphragm electrolysis apparatus (4) under pressure, which comes from a metering pump (7) with a container (9) for dissolving of the salt, there is a device for dissolving moist gaseous products of the electrochemical anode reactions in the fresh water stream to obtain an oxidizing agent solution, a device for stabilizing the excess pressure in the anode compartment (5), a collecting container (14) for the oxidizing agent solution and a device for the metered addition guidance of the catholyte from the separating container (21) of the cathode circuit into the oxidizing agent solution to be synthesized, characterized in that
in einer Zuführungsleitung für das Süßwasser zur Vorrichtung zum Lösen feuchter gasförmiger Produkte der elektrochemischen Anodenreaktionen ein Filter (19) angeordnet ist, vor dem in der Zuführungsleitung für das Süßwasser eine Einrichtung zur dosierten Einbringung von Katholyt aus dem Abscheidebehälter (21 ) des Kathodenkreises in den Wasserstrom, der an den Filter (19) strömt, montiert ist, wobei das Lösen des Salzes im Behälter (9) der Vorrichtung für die Zuführung von wässriger Salzlösung in den Anodenraum (5) in der Oxidationsmittellösung mittels der Einrichtung zur dosierten Zuführung der Oxidationsmittellösung aus dem Sammelbehälter (14) für die Oxidationsmittellösung in den Salzlösebehälter (9) erfolgt, an dessen Ausgang ein Filter (8) angeordnet ist, der mit dem Eingang der Dosierpumpe (7) für die Zuführung der Salzlösung unter Druck in den Anodenraum (5) des Elektrolyseapparates verbunden ist. A filter (19) is arranged in a feed line for the fresh water to the device for dissolving moist gaseous products of the electrochemical anode reactions, in front of which a device for the metered introduction of catholyte from the separating container (21) of the cathode circuit into the water flow in the feed line for the fresh water , which flows to the filter (19), is mounted, the dissolving of the salt in the container (9) of the device for supplying aqueous salt solution into the anode compartment (5) in the oxidant solution by means of the device for metered supply of the oxidant solution from the Collecting container (14) for the oxidizing agent solution into the salt dissolving container (9) takes place, at the output of which a filter (8) is arranged, which with the input of the metering pump (7) for supplying the salt solution under pressure into the anode compartment (5) of the electrolysis apparatus connected is.
PCT/EP2018/078559 2018-10-18 2018-10-18 Electrochemical system for the synthesis of aqueous oxidising agent solutions WO2020078553A1 (en)

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PCT/EP2018/078559 WO2020078553A1 (en) 2018-10-18 2018-10-18 Electrochemical system for the synthesis of aqueous oxidising agent solutions
ES18807868T ES2916459T3 (en) 2018-10-18 2018-10-18 Electrochemical system for the synthesis of an aqueous solution of oxidizing agent
EP18807868.7A EP3867422B1 (en) 2018-10-18 2018-10-18 Electrochemical system for the synthesis of aqueous oxidising agent solutions
EA202100115A EA039722B1 (en) 2018-10-18 2018-10-18 Electrochemical system for the synthesis of aqueous oxidising agent solutions
CN201880098779.1A CN112912544B (en) 2018-10-18 2018-10-18 Electrochemical system for synthesizing an aqueous oxidant solution
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